where k (M− 2 s− 1) can be determined from the
in the pH range 2 to 5, from 5 to 40 °C and 0.01 to 1 M.The effect of pH and ionic strength on the reaction suggest that the rates are due to
where H2A = H2CrO4, HA = HCrO4, H2B = H2SO3 and HB = HSO3. The overall rate expression over the investigated pH range can be determined from
k=kH2A–H2B(αH2A)(αH2B)2+kHA–H2B(αHA)(αH2B)2+kH2A–HB(αH2A)(αHB)2
with kH2A−H2B = 5.0 × 107, kHA–H2B = 1.5 × 106 and kH2A–HB = 6.7 × 107.Fe(III) in the range 1.5 to 20 μM exerts a small catalytic effect on the reaction and significantly lowers the initial concentration of Cr(VI) compared to the nominal value. Contrary to Fe(III), formaldehyde (20 to 200 μM) reacts with S(IV) to form the hydroxymethanesulfonate adduct (CH2OHSO3), which does not react with Cr(VI). Major cations Mg2+ and some minor elements such as Ba2+ and Cu2+ did not affect the rates. The application of this rate law to environmental conditions suggest that this reaction may have a role in acidic solutions (aerosols and fog droplets). This reaction becomes more important in the presence of high Fe(III) and low HMS concentrations, contributing to affect the atmospheric transport of chromium species and the distribution of redox species of chromium, which reach surface water from atmospheric depositions.  相似文献   
8.
Total content and chemical speciation of arsenic in the polychaete Sabella spallanzanii     
Fattorini D  Bocchetti R  Bompadre S  Regoli F 《Marine environmental research》2004,58(2-5):839-843
An unusual feature has been observed in polychaetes regarding their capacity to accumulate high levels of relatively toxic forms of arsenic in specific tissues. Basal levels of arsenic and distribution of its compounds were investigated in tissues of the Mediterranean polychaete Sabella spallanzanii. Particularly high concentrations were measured in the branchial crown (1036+/-136 microg/g d.w.) and chemical speciation revealed that the predominant form was the relatively toxic dimethylarsinate (DMA). These data suggest a potential role of As as anti-predatory strategy in polychaetes.  相似文献   
9.
LightSquared effects on estimated C/N 0, pseudoranges and positions     
Marco Rao  Cillian O’Driscoll  Daniele Borio  Joaquim Fortuny 《GPS Solutions》2014,18(1):1-13
We present experimental results showing the impact of the proposed LightSquared (LS) Long-term Evolution (LTE) signals on both GPS and Galileo civil modulations in the L1/E1 band. The experiments were conducted in radiated mode in a large anechoic chamber. Three Galileo enabled receivers were chosen for the tests, and a state of the art GNSS signal generator was used to simulate both GPS and Galileo signals. The LTE signals were generated by an Agilent Programmable Signal Generator with a license to generate the signals according to the 3GPP LTE FDD standard. The interference impact was measured in terms of a Carrier-to-Noise power spectral density ratio (C/N 0) degradation, in accordance with the methodology which the LS/GPS Technical Working Group (TWG) established by mandate of the FCC. A model for determining the impact of the LS signal on the considered GNSS signals is provided and is validated against experimental data. It is shown that the Galileo E1 Open Service (OS) signal is marginally more susceptible to this form of interference than the GPS L1 C/A signal due to its greater proximity to the lower edge of the L1 band. The impact of LS interference was further analyzed in terms of pseudorange and position errors. Despite its relevance for most GNSS users, this aspect was not considered by the TWG. Measurement and position domain analysis along with the study of the LS impact on the Galileo OS signals are the major contributions. The analysis confirms the results obtained by the TWG and shows that the receiver front-end plays a major role in protecting GNSS signals against RF interference. While it appears that, for now, the LS network will not be deployed, the approach taken and the results obtained herein can be readily adapted for any future terrestrial mobile network that may take the place of LS.  相似文献   
10.
A model for the viscosity of rhyolite as a function of H2O-content and pressure: A calibration based on centrifuge piston cylinder experiments     
Paola Ardia  Daniele Giordano 《Geochimica et cosmochimica acta》2008,72(24):6103-6123
The Newtonian viscosity of synthetic rhyolitic liquids with 0.15-5.24 wt% dissolved water was determined in the interval between 580 and 1640 °C and pressures of 1 atm and 5-25 kbar. Measurements were performed by combining static and accelerated (up to 1000g) falling sphere experiments on water-bearing samples, with high temperature concentric cylinder experiments on 0.15 wt% H2O melts. These methods allowed viscosity determinations between 102 and 107 Pa s, and cover the complete range of naturally occurring magmatic temperatures, pressures, and H2O-contents for rhyolites.Our viscosity data, combined with those from previous studies, were modeled by an expression based on the empirical Vogel-Fulcher-Tammann equation, which describes viscosities and derivative properties (glass transition temperature Tg, fragility m, and activation volume of viscous flow Va) of silicic liquids as a function of P-T-X(H2O). The fitted expressions do not account for composition-dependent parameters other than X(H2O) and reproduce the entire viscosity database for silicic liquids to within 3.0% average relative error on log η (i.e. std. error of estimate of 0.26 log units).The results yield the expected strong decrease of viscosity with temperature and water content, but show variable pressure dependencies. Viscosity results to be strongly affected by pressure at low pressures; an effect amplified at low temperatures and water contents. Fragility, as a measure for the deviation from Arrhenian behavior, decreases with H2O-content but is insensitive to pressure. Activation volumes are always largely negative (e.g., less than −10 cm3/mol) and increase strongly with H2O-content. Variations in melt structure that may account for the observed property variations are discussed.  相似文献   
1 [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] 下一页 » 末  页»
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1.
Integrating analysis of the benthic palaeoecological record with multivariate ordination techniques represents a powerful synergy able to provide an improved characterization of coastal depositional facies in a sequence stratigraphical perspective. Through quantitative analysis of benthic foraminifer, ostracod and mollusc associations from the postglacial succession of Core M3 (Arno coastal plain, Tuscany, Italy), and application of detrended correspondence analysis (DCA) to the mollusc sub‐data set, we offer a refined picture of stratigraphical variations in faunal content from a paralic depositional setting, and reconstruct the palaeoenvironmental gradients that account for such variations. Despite distinct ecological behaviours, and taphonomic and sedimentological constraints, a strong ecological control on meio‐ and macrofaunal biofacies and taxa turnover is documented across the study succession. Amongst all possible mechanisms that may play a role in ‘shaping’ fossil distribution, the ecological signal driven by salinity represents the most prominent factor controlling the composition of fossil associations in the cored succession. Molluscs can even provide outstanding quantitative estimates of palaeosalinity along the sampled core. When plotted stratigraphically, the three fossil sub‐data sets show consistent patterns of vertical evolution that enable prompt identification of the key surfaces for sequence stratigraphical interpretation in otherwise lithologically indistinguishable deposits. The concomitant maximum richness of species with strong marine affinity, paralleled by the highest DCA salinity estimates, allows recognition of the maximum flooding zone, dated to 7.7 cal. ka BP, within a homogeneous succession of outer lagoon clays. These clays are sandwiched between early transgressive, swamp to inner lagoon deposits and overlying prograding coastal?alluvial plain facies.  相似文献   
2.
An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu3SnS4, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu3SnS4 crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)2Cu(II)SnS4 and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.  相似文献   
3.
Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Bécancour, Québec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na-Ca-Cl type, possibly derived from halite dissolution. 87Sr/86Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2-3% contribution of mantle 3He and large amounts of nucleogenic 21Ne and 38Ar and radiogenic 4He and 40Ar. 4He/40Ar and 21Ne/40Ar ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of 40Ar in brines constrain the residence time of Bécancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian-Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian-Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic 40Ar into the brines. The last thermal event that could have facilitated the liberation of 40Ar into fluids and contributed to mantle 3He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Bécancour brines.  相似文献   
4.
5.
Ressi is a small (2.4 ha) forested catchment located in the Italian pre-Alps. The site became an experimental catchment to investigate the water fluxes in the soil–plant–atmosphere continuum and the impact of vegetation on runoff generation in 2012. The elevation of the catchment ranges from 598 to 721 m a.s.l. and the climate is humid temperate. The bedrock consists of rhyolites and dacites; the soil is a Cambisol. The catchment is covered by a dense forest, dominated by beech, chestnut, maple, and hazel trees. The field set up includes measurements of the rainfall in an open area, streamflow at the outlet, soil moisture at various depths and locations, and depth to water table in six piezometers at a 5- or 10-min interval. Samples of precipitation, stream water, shallow groundwater and soil water are collected monthly for tracer analysis (stable isotopes (2H and 18O), electrical conductivity and major ions), and during selected rainfall–runoff events to determine the contribution of the various sources to runoff. Since 2017, soil and plant water samples have been collected to determine the sources of tree transpiration. Data collected in the period 2012–2016 are publicly available. Data collection is ongoing, and the data set is expected to be updated on an annual basis to include the most recent measurements.  相似文献   
6.
Stream water temperature plays a significant role in aquatic ecosystems where it controls many important biological and physical processes. Reliable estimates of water temperature at the daily time step are critical in managing water resources. We developed a parsimonious piecewise Bayesian model for estimating daily stream water temperatures that account for temporal autocorrelation and both linear and nonlinear relationships with air temperature and discharge. The model was tested at 8 climatically different basins of the USA and at 34 sites within the mountainous Boise River Basin (Idaho, USA). The results show that the proposed model is robust with an average root mean square error of 1.25 °C and Nash–Sutcliffe coefficient of 0.92 over a 2‐year period. Our approach can be used to predict historic daily stream water temperatures in any location using observed daily stream temperature and regional air temperature data.  相似文献   
7.
The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔHapp of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression
−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]2
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